JP2017533326A - 潤滑剤組成物中のアルコキシル化アミド、エステル、および摩耗防止剤 - Google Patents
潤滑剤組成物中のアルコキシル化アミド、エステル、および摩耗防止剤 Download PDFInfo
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- JP2017533326A JP2017533326A JP2017523526A JP2017523526A JP2017533326A JP 2017533326 A JP2017533326 A JP 2017533326A JP 2017523526 A JP2017523526 A JP 2017523526A JP 2017523526 A JP2017523526 A JP 2017523526A JP 2017533326 A JP2017533326 A JP 2017533326A
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Images
Classifications
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
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- C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M141/10—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic phosphorus-containing compound
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
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- C10M133/16—Amides; Imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/12—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic compound containing atoms of elements not provided for in groups C10M141/02 - C10M141/10
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
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- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
- C10M2205/0285—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract
Description
本開示は概して、アルコキシル化アミドと、エステルと、リン、モリブデン、またはそれらの組み合わせを含む摩耗防止剤とを含む潤滑剤組成物用の添加剤パッケージ、基油と、アルコキシル化アミドと、エステルと、リン、モリブデン、またはそれらの組み合わせを含む摩耗防止剤とを含む潤滑剤組成物、およびアルコキシル化アミドと、エステルと、リン、モリブデン、またはそれらの組み合わせを含む摩耗防止剤とを含む潤滑剤組成物で内燃機関を潤滑する方法に関する。
潤滑剤組成物の性能は添加剤の使用によって改善することができる。たとえば、摩耗を軽減し、燃料経済性を高めるために、ある摩耗防止剤が潤滑組成物に添加されてきた。しかしながら、燃料経済性におけるさらなる改善が望まれる。
本開示は、潤滑剤組成物用の添加剤パッケージを提供する。添加剤パッケージは:
(A)一般式(I):
(B)一般式(II):
を有するエステルと、
(C)リン、モリブデン、またはそれらの組み合わせを含む摩耗防止剤と
を含む。
本開示は、潤滑剤組成物用の添加剤パッケージを提供する。添加剤パッケージまたは潤滑剤組成物は、アルコキシル化アミドと、エステルと、リン、モリブデン、またはそれらの組み合わせを含む摩耗防止剤とを含む。潤滑剤組成物は基油も含む。添加剤パッケージを潤滑剤組成物に添加してもよい。添加剤パッケージおよび(添加剤パッケージの添加に際して)結果として得られる潤滑剤組成物のどちらも本開示ではまとめて考慮し記載する。本開示全体にわたって添加剤パッケージに関するほとんどの言及は、潤滑剤組成物の記載にも当てはまることが理解されるべきである。たとえば、潤滑剤組成物は、異なる量であるが、添加剤パッケージと同じ成分を含んでもよいし、または排除してもよいことが理解されるべきである。
一般式(XIII)中、Lは、化合物を油中に溶解可能または分散可能にするために十分な数の炭素原子を有する有機基を有する、独立して選択されたリガンドである。一般式(XIII)中、nは1〜4の数である。また、一般式(XIII)中、kは4〜7の数である。さらに、一般式(XIII)中、Qは、水、アミン、アルコール、ホスフィン、およびエーテルなどの中性電子供与性化合物の群から選択される。また、一般式(XIII)中、zは0〜5の数である。ある実施形態では、少なくとも21個、少なくとも25個、少なくとも30個、または少なくとも35個の総炭素原子が、モリブデンを含む摩耗防止剤の全てのリガンドの有機基に存在しなければならない。
アルコキシル化アミドおよびエステルの形成のための例示的方法1
A ココナッツ油ジエタノールアミド混合物を形成するための縮合反応
ココナッツ油(3.80kg、5.78mol)を反応器に添加し、約130℃に加熱した。ジエタノールアミン(DEA)(1.22kg、11.6mol、2当量)を添加し、そして結果として得られた混合物を、さらに6時間撹拌しながら約130℃の反応温度を維持した。生成物は粘稠性の黄色から褐色油状物(5.01kg)であり、これを精製することなくアルコキシル化反応で使用した。
ステップAのジエタノールアミド反応生成物(869g、2.02mol)をアミン触媒(4.9g N,N−ジメチルエタノールアミン、0.06mol、0.5質量%)と混合した。結果として得られる混合物を約110℃に加熱した。プロピレンオキシド(117g、2.02mol、1.0当量)を添加し、混合物を反応温度でさらに12時間撹拌した。減圧下および/または窒素ガスでフラッシュすることによって未反応プロピレンオキシドを除去して、反応生成物を得た。
A ココナッツ脂肪酸ジエタノールアミド混合物を形成するための縮合反応
ココナッツ脂肪酸(3.05kg、14.4mol)を反応器に入れ、約80℃に加熱した。ジエタノールアミン(1.52kg、14.4mol、1.0当量)を添加し、結果として得られる混合物を約150℃の反応温度に加熱し、次いでさらに8時間撹拌した。生成物は粘稠性の黄色から褐色の油状物(3.95kg)であり、これをさらに精製することなくアルコキシル化反応で使用した。
ステップAのジエタノールアミド反応生成物(495g、1.72mol)をアミン触媒(3.0g Ν,Ν−ジメチルエタノールアミン、0.03mol、0.5質量%)と混合した。結果として得られる混合物を約115℃に加熱した。プロピレンオキシド(100g、1.72mol、1.0当量)を添加し、混合物を約115℃でさらに12時間撹拌した。減圧下および/または窒素でフラッシュすることによって未反応プロピレンオキシドを除去して、反応生成物を得た。
A 摩擦係数およびボールスカー直径評価I
基油、アルコキシル化アミド、エステル、および摩耗防止剤を含む潤滑剤組成物の摩擦係数およびボールスカー直径を評価した。潤滑剤組成物の摩擦係数を、修正ASTM D6079法にしたがって測定した。修正ASTM D6079法は摩擦係数を測定するために高周波往復動リグ(HFRR)を利用する。測定する間、HFRRは1mmのストロークで10Hzにて往復運動した。100℃の温度にて標準的HFRSSP鋼球を使用して400グラムの負荷で120分間測定を実施した。潤滑剤組成物のボールスカー直径をレーザー表面形状測定装置によって測定した。
基油、アルコキシル化アミド、エステル、および摩耗防止剤を含む潤滑剤組成物の摩擦係数およびボールスカー直径を、比較摩擦調整剤を含む潤滑剤組成物に対してさらに評価した。それぞれの潤滑剤組成物の摩擦係数を、修正ASTM D6079法に従って測定した。修正ASTM D6079法は、摩擦係数を測定するために高周波往復動リグ(HFRR)を利用した。測定中、HFRRは1mmのストロークで10Hzにて往復運動した。測定は、標準的HFRSSP鋼球を使用して400グラムの負荷で120分間100℃の温度にて実施した。それぞれの潤滑剤組成物のボールスカー直径をレーザー表面形状測定装置によって測定した。
基油、アルコキシル化アミド、エステル、および摩耗防止剤を含む潤滑剤組成物のトラクション係数を、比較摩擦調整剤を含む潤滑剤組成物に対して評価した。それぞれの潤滑剤組成物のトラクション係数を、ミニ・トラクション・マシン(Mini−Traction Machine:MTM)、具体的にはPCS Instruments社から入手したMTM2を利用することによって測定した。測定中、標準的鋼球(19.05mm)およびディスク(46mm)をMTMで利用した。MTMの負荷を1GPaに設定し、潤滑剤組成物を125℃に予熱した。それぞれの潤滑剤組成物のトラクション係数は、25%スライド/ロール比を利用して0〜2000mm/sの速度から測定した。
潤滑剤組成物を利用した車両の燃料経済性の改善は、低負荷車両の燃料経済性の測定のためにU.S.EPAによって開発されたシャーシ・ダイナモメーター・ドライビング・スケジュールであるHwFETにしたがって測定した。2012年製ホンダ・シビック(1.8L PFI)、2004年製マツダ3(2.0L PFI)、2012年製ビューイック・リーガル(2.0L GDI)、および2012年製フォード・エクスプローラ(2.0L TGDI)を測定のために使用した。
エンジン動力計による燃料消費評価を、潤滑剤組成物を用いたエンジンに対して実施した。
摩擦に関する概念を判定するためにHFRRおよびMTMを利用した前述の評価は、通常、ベンチテストであると考えられる。これらの試験を利用して、摩擦に関する概念について多数の潤滑剤組成物を時速かつ費用効率的にスクリーンすることができる。しかしながら、上記評価を全体として見ると、摩擦に関する概念は、燃料経済性と必ずしも相関するとは限らない。たとえば、ベンチテストを使用してアルコキシル化アミドとエステルとの混合物を含む潤滑剤組成物に対してグリセロールモノオレエートを含む潤滑剤組成物を評価するだけの場合、グリセロールモノオレエートを含む潤滑剤組成物はアルコキシル化アミドとエステルとの混合物を含む潤滑剤組成物と比較して、摩擦に関連する概念に基づいて燃料経済性の増加を示すという誤った判断をする可能性がある。車両の燃料経済性を測定するためにOEMによって通常用いられる上記HwFET評価の観点から、アルコキシル化アミドとエステルとの混合物を含む潤滑剤組成物は、エンジンにおいてグリセロールモノオレエートを含む潤滑剤組成物と比較して、エンジンにおける燃料経済性の増加を示す。
請求項3は請求項1または2に従属し得る;
請求項5は請求項1から4のいずれか1項に従属し得る;
請求項6は請求項1から5のいずれか1項に従属し得る;
請求項8は請求項1から7のいずれか1項に従属し得る;
請求項10は請求項1から9のいずれか1項に従属し得る;
請求項12は請求項1から11のいずれか1項に従属し得る;
請求項13は請求項1から12のいずれか1項に従属し得る;
請求項14は請求項1から13のいずれか1項に従属し得る;
請求項15は請求項1から14のいずれか1項に従属し得る;
請求項16は請求項1から15のいずれか1項に従属し得る;および
請求項17は請求項1から16のいずれか1項に従属し得る。
Claims (21)
- 前記摩耗防止剤がリンを含む、請求項1に記載の潤滑剤組成物。
- 前記摩耗防止剤がジアルキルジチオリン酸亜鉛である、請求項2に記載の潤滑剤組成物。
- 前記アルコキシル化アミドのR2およびR3の少なくとも1つがプロポキシ基を含む、請求項1から3のいずれか1項に記載の潤滑剤組成物。
- 前記アルコキシル化アミドおよび前記エステルのR1がそれぞれ独立して、直鎖または分枝、飽和または不飽和C7〜C23脂肪族ヒドロカルビル基である、請求項1から3のいずれか1項に記載の潤滑剤組成物。
- 前記アルコキシル化アミドまたは前記エステルのR1がヒドロキシル基を含む、請求項8に記載の潤滑剤組成物。
- R1がそれぞれ独立して、直鎖または分枝、飽和または不飽和C7〜C23脂肪族ヒドロカルビル基であり;
R5がそれぞれ独立して、エチル基またはプロピル基であり;
R6がそれぞれ独立してプロポキシ基であり;
nが0〜5の整数であり;
mが0〜5の整数であり;
1≦(n+m)≦5であり;
qが0〜5の整数であり;
qが0である場合、pは1〜5の整数であり;
qが>0である場合、pは1〜5の整数であり;
1≦(p+q)≦5であり;
前記潤滑剤組成物は、前記アルコキシル化アミドおよび前記エステルを、前記エステルの、前記アルコキシル化アミドに対する質量比70未満:30で含む、請求項10に記載の潤滑剤組成物。 - 前記基油がクランクケース潤滑剤組成物としてさらに定義される、請求項1から3のいずれか1項に記載の潤滑剤組成物。
- 前記基油がAPIグループI油、APIグループII油、APIグループIII油、APIグループIV油、またはそれらの組み合わせを含み、前記基油が、ASTM D445にしたがって100℃で試験した場合、1〜20cStの範囲の粘度を有する、請求項1から3のいずれか1項に記載の潤滑剤組成物。
- 前記アルコキシル化アミドおよび前記エステルを、前記エステルの、前記アルコキシル化アミドに対する質量比50未満:50で含む、請求項1から3のいずれか1項に記載の潤滑剤組成物。
- 前記アルコキシル化アミドが、前記潤滑剤組成物の総質量を基準として0.01〜20質量%の量で存在する、請求項1から3のいずれか1項に記載の潤滑剤組成物。
- 前記エステルが、前記潤滑剤組成物の総質量を基準として0.01〜20質量%の量で存在する、請求項1から3のいずれか1項に記載の潤滑剤組成物。
- 前記摩耗防止剤が前記潤滑剤組成物の総質量を基準として0.001〜30質量%の量で存在する、請求項1から3のいずれか1項に記載の潤滑剤組成物。
- 前記摩耗防止剤がジアルキルジチオリン酸亜鉛である、請求項18に記載の方法。
- 前記摩耗防止剤がジアルキルジチオリン酸亜鉛である、請求項20に記載の添加剤パッケージ。
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US62/205,297 | 2015-08-14 | ||
PCT/US2015/058009 WO2016069873A1 (en) | 2014-10-31 | 2015-10-29 | Alkoxylated amides, esters, and anti-wear agents in lubricant compositions |
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EP3212746A4 (en) | 2018-06-20 |
US9909081B2 (en) | 2018-03-06 |
US9920275B2 (en) | 2018-03-20 |
US10246661B2 (en) | 2019-04-02 |
US20160208187A1 (en) | 2016-07-21 |
EP3212746A1 (en) | 2017-09-06 |
US20180171257A1 (en) | 2018-06-21 |
WO2016069873A1 (en) | 2016-05-06 |
US20170096615A1 (en) | 2017-04-06 |
EP3212746B1 (en) | 2022-03-16 |
JP7009213B2 (ja) | 2022-02-10 |
CN107109279B (zh) | 2020-12-25 |
CN107109279A (zh) | 2017-08-29 |
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